Condensation products of the benzanthrone series and process for their preparation



Patented Nov. 17, 1953 CONDENSATION PRODUCTS OF THE BENZANTHRONE SERIES AND PROC- ESS FOR THEIR PREPARATION James M. Straley, Kingsport, Tenn., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 4, 1950, SerialNo. 153,996

- 4 Claims.

This invention relates to a process for preparing condensation products of the benzanthrone series and to certain of the benzanthrone compounds as new compounds.

In accordance with the process of my invention a IO-methyleneanthrone compound which is unsubstituted in at least one of the 4- and positions is condensed with 1,3-cyclohexadiene to obtain new valuable vat dye intermediates which are probably B22, Bz2'-ethylene-bridgeddibenzanthronyl compounds. These latter compounds are fused by means of KOH or NaOH to form new vat dye compounds which in turn are oxidized to form the final vat dye products of my new process.

IO-methyleneanthrone has the probable formula:

The numbering given is that employed herein.

It is an object of my invention to provide new valuable vat dye intermediates which are probably B22, Bz2-ethylene-bridged dibenzanthronyl compounds. Another object is to provide new valuable vat dyes which are probably dibenzanthrone compounds in which the 16- and 17- positions are bridged by an ethylene linkage. A further object is to provide valuable vat dyes which are probably dibenzanthrone compounds in which the 16- and 1'7- positions are bridged by a -CI-I=CH linkage. Another object is to provide a satisfactory process for the preparation of the compounds of the invention.

In carrying out the process of the invention a -methyleneanthrone compound which is unsubstituted in at least one of the 4- and 5- positions is condensed with 1,3-cyclohexadiene in the presence of a mild oxidizing agent such as oxygen and nitrohydrocarbons and their derivatives. A number of the nitrohydrocarbon type of oxidizing agents are disclosed hereinafter. Nitroalkanes, aqueous solutions of nitrobenzene sulfonic acids and aromatic nitrocompounds differ only in degree and not in kind of influence. Although nitroalkanes such as nitromethane, nitroethane, n-nitropropane (CHsCHzCHzNOz) and n-nitrobutane (CHsCHzCHzCI-IzNOz), for example, and although nitrobenzene sulfonic acids such as o-nitrobenzene sulfonic acid, mnitrobenzene sulfonic acid and p-nitrobenzene sulfonic acid, for example, can be used, I prefer to employ aromatic nitrohydrocarbons such as nitrobenzene, o-nitrotoluene, m-nitrotoluene, pnitrotoluene, a nitro xylene such as 2-nitro-1,3- dimethylbenzene, l-nitro-1,2-dimethylbenzene, etc.; a-nitronaphthalene, fi-nitronaphthalene and a.-nitromethylnaphthalene, for example.

The use of a strong oxidizing agent, such as potassium permanganate, nitric acid or potas- 'sium dichromate, for example, should be avoided in this phase of my invention. If strong oxidizing agents were used, particularly at high temperatures, side reactions would occur, due to either the ease of oxidizing methyleneanthrone compounds to anthraquinone compounds or possible destruction of the desired reaction product, thereby seriously lowering the yield.

The reaction temperature does not. appear to be critical as the products can be obtained at ordinary temperatures as well as at high temperatures. Temperatures of from about 25 C. to about 200 C., for example, can be employed. Temperatures of from about C. to about 0. appear most suitable and are preferred. Where low temperatures are employed, a longer reaction time is required. Temperatures in excess of 200 0. appear to reduce the yield and to cause contamination, apparently by polymerization of the methyleneanthrone competing with the desired addition reaction.

The reaction, as illustrated with reference to IO-methyleneanthrone, is believed to proceed as follows:

CH2 E G H2O CH [O] I A H20 H A H 3 IO-methyleneanthrone compounds that can be employed include, for example, IO-methyleneanthrone, 1D-methylene-2-chloroanthrone, methylene-l-methylanthrone, IO-methylenelbromoanthrone; lq-methylene-l -fiuoroanthi one, 10-methylene-3methylanthrone, lfl methylene- 3-chloroanthrone, 10-methylene-2-methylanthrone and IO-methylene-l-chloroanthrone. As previously indicated, by the action of cause tic alkali such as KOI-I or vat dye intermediates of the invention, newvat; dye compounds are obtained. This reaction, as

illustrated with reference tothe unsubstituted vat dye intermediate is believed to take as follows:

The and 2' positions of the starting compound must be unsubstituted. By the use of a starting compound which is substituted, for example, with a chlorine atom, a bromine atom, a fluorine atom or a methyl group, substituted vat dye compounds are obtained. The positions of the substituent or substituents in the vat dye obtained are determined by the position or positions occupied by the substituent orsubstituents in the starting compound.

The new vat dye compounds which in,their unsubstituted form have the probable Formula IV are easily obtained by introducing the'new intermediates which in their unsubstituted form have the probable Formula III into melts of KOI-I or NaOH at temperatures of from about 105 C. to about 160 C. While any of the standard conditions of caustic fusions used in the vat dye in dustry appear to be suitable, the use of ethyl or methyl alcohol potassium hydroxide melting at temperaturesof about 130C. to about 155 C. appearsadvantageous and is preferred.

The new vat dye compounds thus obtained dye cotton well from a hot, stronglyalkaline vat. The dyeings obtained are attractive shades oi blue and possess excellent wash-fastness. However, as explainedv hereinafter, these new vat dye compounds which will be referred to herein as intermediate vat dye compounds are readily converted to more permanent dyestufis, i. e., the final products of the presentinvention.

The'final products of the invention are obtained by oxidizing the intermediate vat dye compounds which in their unsubstituted form have the For- NaOH.1up(-m theih'ewuuw mulaIV. Thegoxidation can be carried out in a number pfiways. Thus oxidation can be effected by heatingthe intermediate vat dye in air at temperaturesabove :169 C. either en masse or on the fiben The final products can also be obtained by incorporating an oxidizing agent into the caustic alkali melts used in the formation of the intermediate vat dye compounds or the intermediate vat dye compounds can be oxidized to the final vat dye products by means of chemical oxidizing agents. Further, exposure to strong ultraviolet light, such as that used in apparatus for testing the light fastness of dyeings, will also effect the transformation of the intermediate vat dye compounds to the final products.

The conversion ofthe new intermediate vat dye compoundsto the final vat dye compounds is illustrated by the following equation wherein an unsubstituted intermediate vat dye compound is employed as the starting compound.

It is to be clearlyunderstood that the final products maycontainsubstituents and it is here noted, for example, that the halogenated vat dye compounds of Examples 16 and 18 give a more pleasing shadeofred than the corresponding unsubstituted vat dye compound.

The following examples illustrate the compoundsof our invention and the manner in which the process of, ourinvention is carried out. Parts are expressed asparts by Weight.

Preparation of cat. dye intermediates.

EXAMPLE 1 I ture refiuxed'for 1 hour.

'o-nitrotoluene for 6 hours.

,5 EXAMPLE 2 10 parts of IO-methyleneanthrone, 2 parts of 1,3-cyclohexadiene, 40 parts of acetic acid and 5 parts of acetic anhydride were refluxed together for 6 hours after which the reaction mixture was cooled and filtered. The reaction product was recovered on the filter and dried. The product obtained was the same as that obtained in Example 1. The yield of product was about 35%.

EXAMPLE 3 be used), allowed to cool to room temperature and then filtered. A heavy crop of bright yellow crystals having the same properties and formula as the product of Example 1 was obtained. The yield of product was about 68%. A solution of the product in concentrated sulfuric acid has a bluish-red color.

EXAMPLE 4 20 parts of a methyl methyleneanthrone prepared from the 2-methylanthrone of Ber. 38, 1792 T (1905) were heated and stirred at 170 C.-180 C.

with 5 parts of 1,3-cyclohexadiene in 80 parts of The reaction mixture was then cooled to 80 C., diluted with an equal volume of ethyl alcohol (methyl alcohol can also be used), allowed to cool to room temperature and then filtered. The product obtained is a yellow-brown powder melting above 360 C. and soluble in concentrated sulfuric acid with a red color.

EXAIVIPLE 5 22 parts of a 10-methylene-dichloroanthrone prepared from lA-dichloroanthrone (Ber. 162,

1971 [1929]) were heated and stirred at 170 C.-

180 C. with 5 parts of 1,3-cyclhexadiene in 80 Q parts of o-nitrotoluene for 6 hours. The reaction mixture was then cooled to 80 C., diluted with an equal volume of ethyl alcohol (methyl alcohol can also be used), allowed to cool to room temperature and then filtered. The product obtained is a brown amorphous material subliming with some decomposition at about 360 C.

EXAMPLE 6 20 parts of a 10-methylenechloroanthrone (probably 10-methylene-l-chloroanthrone), prepared from 1-chloro-9-anthrone [J. C. S. 123, 2553], in 100 parts of nitrobenzene were heated to 180 C. 6 parts of 1,3-cyc1ohexadiene in 10 parts of nitrobenzene were gradually added over a period of 30 minutes with stirring at a temperature of 185 C.-190 C. The temperature was maintained at 180 C.190 C. for 3.5 hours longer, after which 4 parts of 1,3-cyclohexadiene were added and the reaction mixture refluxed for 1 hour. The reaction mixture was then cooled to 80 0., diluted with an equal volume of ethyl alcohol, allowed to cool to room temperature and then filtered to recover the desired reaction prodnot. The product obtained is a yellow powder 6 dissolving in concentrated sulfuric acid with a red color.

EXAMPLE '7 20 parts of a 10 methylenemethylanthrone (probably 10-methylene-1-methylanthrone) prepared from 1-methyl-9-anthrone were reacted with parts of 1,3-cyclohexadiene exactly in accordance with the procedure described in Example 4. A brown product was obtained.

Preparation of intermediate vat dyes- EXAMPLE 8 100 parts of the condensation product of 10- methyleneanthrone and 1,3-cyclohexadiene obtained as in Examples 1, 2 or 3 were gradually added over a period of about minutes at 125 C.-130 C. to a smooth melt prepared from 500 parts of flake potassium hydroxide and 500 parts of ethyl alcohol. The temperature was allowed to rise to 140 C. in about 30 minutes by distillation of the alcohol. The temperature was held at 140 C.-145 C. for 2 hours after which the reaction mixture was drowned in water and airblown at C. to isolate the dyestuff. About 90-95 parts of a blue powder, dissolving in concentrated sulfuric acid with a cherry-red color and a slight blue-red fluorescence, were obtained. With alkaline hydrosulflte it forms a reddishviolet vat and cotton dyed therein is colored a pleasing blue after air-oxidation and soaping.

EXAMPLE 9 parts of the product of Example '7 were treated exactly in accordance with the procedure described in Example 8. The product obtained is a blue powder which dyes cotton from an alkaline hydrosulflte vat blue shades which are slightly duller than those obtained with the dye product of Example 8.

EXAMPLE 10 some of the chlorine atoms initially present in the product of Example 5 have been replaced by hydroxyl groups. This replacement is believed to take place during the fusion operation of this example.

Preparation of final products EXAMPLE 11 17 parts of the condensation product obtained as described in Example 3 were added at C.- C. to a melt prepared from parts of potassium hydroxide and 150 parts of ethyl alcohol. The reaction mixture was then heated to 150 C. and 20 parts of sodium nitrite were added. The temperature rose sharply and after the reaction had subsided, the reaction mixture was drowned in water, blown with air and filtered. 15.5 parts of a reddish-brown powder, dissolving to a violet solution in concentrated sulfuric acid without fluorescence was obtained. It dyes cotton from a blue vat a rather dull red or reddishbordeaux color which is very fast, especially with respect to light.

- 7 EXAMPLE 12 17 parts of the condensation product obtained as described in Example 3' were treated exactly as described in Example 11- except that parts of; potassium chlorate were'used inplace of sodium nitrite, The same dyestuffwas obtained.

Exist/11 m 13 17- parts of the condensation product obtained as described in Example 3 were added at 130 C.-135 C. to a melt prepared from 150 parts of potassium hydroxideand 150 parts of ethylalcohol; The reaction mixture wasthen heated to 150 C.155 C. and-maintained at this-temperat'ure', while stirri'ngyfor 2 hours. Following" this, the reaction mixture was drowned in' water, blown-with air and filtered to obtain ablue vat dyestuff which was suspended in about 50- parts o'f'wa'ter. partsof sodium hypochlorite solution' (about 5% active chlorine) were added to the dye suspension and thereactionmixtu're was brought to 90 C.-:95 C.- and maintained at this temperature for 3 to 4 hourswith good stirring. The bright reddish-brown dyestufi formed was recovered by'filtration, washed with water and dried. A yield of 14.9 parts of apparently the identical product of Examples 11 and 12' was obtained. 7

Th'e'reaction can be'ca'rried out equally well using a mixture of sodium chlorate and hydrochloric acid in place'ofsodium hypochlorite.

EXAMPLE 14 Sample" Of the blue" dyestufi' Obtained as de- ,scribed in Example 9 was finely ground and heated in theair for 8 to 10 hours at l90'C.-200 C. The colorchang'ed slowly toa reddish b'rown. The product obtained dyes"c'ottoii" from a blue vat a. reddish-bordeau'x' colon'which is very fast, especially with respect to light.

swateri of-cotton fabric dyed-withthe product of Example 85 was placed 111 a-fadeometer and exposed until the colo'r of the fabric changed to thatobtained by dyeing a cotton-fabric from'a vat with'the dyestufif of Example 13. This requires 10 to ethos-rs depending upon the-concentration of the dyein'g. The reddish dyeing so produced matches in light-fasthess the dyeings obtainedwith'the dyestuff of Example 13.

EXAMPLE 16 EXAMPLE 17 parts of the dyestuif obtained as-described in Example 13 were finely ground and suspended in 300 parts of nitrobenzene at 50 C. 40 parts of nitric acid (sp; gr. 1.49) were added andthe reaction mixture was'stirred for several hours at 60 C.- C. Then the reaction mixture was poured into alkalinewat'er and the nitrobenzene was removed by steam distillation. The reaction mixture was then filtered and the reaction product recovered on'the filter washed with water and dried. A yield'of 52 parts of a nitrated vat dyestuif was obtained-in the form of a dark powder. It vat dyed cotton a rather dull violet. The light-fastne'ss' of the'dyeings obtained on cotton was excellent.

EXAIVIPLE 18 20 parts of the product obtained as described in Example 14 were refluxed and stirred under an eiiicient condenser with 20 parts of bromine, 500 parts of trichlorobenzene and 0.1 part of iodine for 4 hours. The reaction mixture was cooled, filtered, and the product recovered on the filter was washed with benzene. A yield of 16 parts of a bromine containing vat dyestufi which gives a much bluer solution in concentrated H2504 (sp. gr. 1.83) and a redder dyeing on cotton than does the starting material was obtained.

Dyeing with the vat dye compounds of the invention is performed according to the usual strong-alkali vat procedure. Dyeing can be carried out as follows:

0.65 gram of dyestuff is well ground with a few drops ofmonopol oil' (sulfonated castor-oil) and rinsed into a dye-bath. The dye-bath is brought to a total volume of cc., using soft water, and 0.54 grain of NaOH and 0.75-1 gram of sodium hydrosulfite are added. The temperature oi the dye-bath is raised to 50 C. and 5 grams of a well wet-out cotton goods are entered and dyed at 50 C.-55 C. for lhour. The dyed cloth is removed, rinsed and hung in air until oxidation is ommas, The dyeings are finished by a ZOminu'te' boil in a 0.5% aqueous sodium carbonate solution, rinsing with water and drymg.

While the manner in which my new vat dye compounds are applied to cotton, for example, constitutes no part of my invention, it will be understood that thed'yeing procedure given above is'merely illustrative and not limitative of the manner in which they may be" applied to cotton oods.

While methylene'anthrone and a number of substituted methylene'arithrone compounds are known compounds, it is here noted that methyleneanthrone can be prepared asd'esc'ribed by K. H. Meyer, Liebigs Annalen, vol. 420, page (1920). Substituted methyleneanthrone compounds can be prepared by the method just referred to for the preparation of methyleneanthrone by" the use-of a substituted anthrone compound in place of'anthrone.

. I claim:

1.. The compounds selected from the groupconsisting of compounds having the formulas:

and

wherein X and X each represents the same member selected from the group consisting of a hydrogen atom, a bromine atom, a fluorine atom and a methyl group, Y represents a chlorine atom and each n represents the same small whole number selected from the group consisting of 1 and 2.

2. The compounds having the formula:

A. A Y

c c v wherein Y and Y each represents a, chlorine atom.

3. The compounds having the formula:

wherein X and X each represents a methyl group.

4. The compound which has the probable 15 formula:

OTHER REFERENCES 0. A., vol. 40, page 4682 35 Gilman, Organic Chemistry. An Advanced Treatise. vol. I, pages 685-687 (1943), New York, John Wiley and Sons. 

1. THE COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FORMULAS: 